CN109742447B - Preparation method of lithium difluorobis (oxalato) phosphate solution - Google Patents
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Abstract
The invention provides a preparation method of a lithium difluorobis (oxalato) phosphate solution, which comprises the following steps: (1) reacting dichlorodimethylsilane with oxalic acid in the presence of a non-aqueous solvent to generate dimethylsilyl oxalate; (2) and (2) adding lithium hexafluorophosphate into the reaction solution obtained in the step (1) to react to obtain the lithium difluorobis (oxalato) phosphate solution. The preparation method is simple and practical, and can be used for industrial production, the prepared lithium difluorobis (oxalate) phosphate solution can be directly used as a non-aqueous electrolyte battery additive, and the prepared lithium difluorobis (oxalate) phosphate solution contains less chlorine compounds and free acids, wherein the chlorine compounds are less than 5 mass ppm by chlorine concentration, and the free acids are less than 200 mass ppm by hydrofluoric acid converted acid concentration.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of a lithium difluorobis (oxalato) phosphate solution.
Background
Lithium difluorobis (oxalato) phosphate is used as an additive for nonaqueous electrolyte batteries such as lithium ion batteries and lithium ion capacitors. After the additive is added into the electrolyte, the battery has excellent low-temperature resistance, and a stable solid electrolyte interface film can be formed on the surfaces of the anode and the cathode of the battery, so that the cycle performance of the battery is improved. The following methods are mainly used for the production of lithium difluorodicarboxylate phosphate.
Patent No. CN200980145463 proposes mixing oxalic acid and lithium hexafluorophosphate at a certain molar ratio, and adding SiCl thereto4A method of effecting the reaction. In this method, SiCl having extremely high reactivity is used4As a reaction auxiliary agent, the reaction cannot be precisely controlled, and HCl and SiF are generated in the reaction process4The mixed gas is difficult to separate and cannot be utilized, thereby affecting the industrialization.
Disclosure of Invention
The invention aims to provide a simple, practical and industrially-producible preparation method of lithium difluorobis (oxalato) phosphate solution.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of lithium difluorobis (oxalato) phosphate solution comprises the following steps:
(1) reacting dichlorodimethylsilane with oxalic acid in the presence of a non-aqueous solvent to generate dimethylsilyl oxalate;
(2) and (2) adding lithium hexafluorophosphate into the reaction solution obtained in the step (1) to react to obtain the lithium difluorobis (oxalato) phosphate solution.
The oxalic acid used in the preparation method of the lithium difluorobis (oxalato) phosphate solution is a dried product. The drying method is not particularly limited, and vacuum drying, chemical dehydration, or the like can be used. The water content in the dried oxalic acid is preferably 300 mass ppm or less.
In the present invention, the concentration of oxalic acid in the nonaqueous solvent at the initial stage of the reaction is not particularly limited, and may be any concentration, and the lower limit is preferably 1%, more preferably 5%, and the upper limit is preferably 20%, more preferably 15%. When the concentration is less than 1%, the obtained lithium difluorobis (oxalato) phosphate solution is relatively dilute, and therefore, it requires a long time for concentration when used as an electrolyte solution for a nonaqueous electrolyte battery, and therefore, it is uneconomical. On the other hand, if the content exceeds 20%, the oxalic acid is not completely dissolved, and the reaction is not easily completed, which is not preferable.
Preferably, the feeding molar ratio of the oxalic acid to the dichlorodimethylsilane is 1: 1-2, and more preferably 1: 1.2-1.6. When the amount of dichlorodimethylsilane is less than 1 mole relative to 1 mole of oxalic acid, the reaction of oxalic acid is incomplete, and an impurity removal operation is required in the later stage, and the nonaqueous electrolyte additive cannot be used. When the amount of dichlorodimethylsilane is more than 2 moles with respect to 1 mole of oxalic acid, the waste of materials is caused, which is uneconomical.
Preferably, the feeding molar ratio of the oxalic acid to the lithium hexafluorophosphate is 1: 0.4-0.6, and more preferably 0.5-0.55 molar amount. When the addition ratio is less than 0.4 mol, lithium tetrafluoro oxalate phosphate is produced as a by-product, which affects the purity of the product. When the addition ratio is more than 0.6 molar mass, the concentration of the free acid in the resulting solution becomes high, and thus it is difficult to use the solution as an additive for a nonaqueous electrolyte battery.
Preferably, the nonaqueous solvent is one or more of cyclic carbonate, chain carbonate, cyclic ester, chain ester, cyclic ether, chain ether and nitrile.
Specific examples thereof include cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate; chain carbonates such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate; cyclic esters such as γ -butyrolactone and γ -valerolactone; chain esters such as ethyl acetate and methyl propionate; cyclic ethers such as tetrahydrofuran and tetrahydropyran; chain ethers such as diethyl ether, diisopropyl ether, and 1, 2-dimethoxyethane; nitriles such as acetonitrile and propionitrile.
The solvent of the present invention preferably uses a dehydrated product. The water concentration in the nonaqueous solvent used in the present invention is preferably 100 mass ppm or less. The nonaqueous solvent used in the present invention may be used alone, or two or more kinds may be mixed in an arbitrary combination and an arbitrary ratio depending on the use.
Preferably, the reaction temperature in the step (1) is 50-100 ℃, and more preferably in the range of 69-80 ℃. When the reaction temperature is lower than 50 ℃, the reaction time increases, which is uneconomical. In addition, when the reaction temperature is higher than 100 ℃, the reaction causes loss of dichlorodimethylsilane material, and high-boiling point chlorine compounds are generated, so that the non-aqueous electrolyte additive cannot be used.
Preferably, in the step (1), after the reaction between dichlorodimethylsilane and oxalic acid is finished, degassing and impurity removal are carried out.
Further preferably, the temperature for degassing and removing impurities is 70-100 ℃, and more preferably 80-90 ℃. The degassing temperature is lower than 70 ℃, the concentration of chlorine compounds in the reaction liquid is high, and the chlorine compounds cannot be used as the nonaqueous electrolyte additive. The degassing temperature is higher than 100 ℃, so that the solution can be subjected to bumping, and the loss of materials is caused.
Absorbing HCl obtained by degassing and impurity removal in the step (1) by water to form a hydrochloric acid solution with low impurity content; (CH) liberated in step (2)3)2F2Si is absorbed by KOH solution to form high-purity and layered linear polysiloxane liquid and KF aqueous solution.
Preferably, the reaction temperature in the step (2) is 20-50 ℃, and more preferably 30-40 ℃. When the reaction temperature is lower than 20 ℃, the reaction time increases, which is uneconomical. When the reaction temperature is higher than 50 ℃, the concentration of free acid in the solution is high, and the solution cannot be used as an additive for nonaqueous electrolytic solutions.
In this reaction, since the starting dichlorodimethylsilane and the product lithium difluorobis (oxalato) phosphate react with water, the reaction is preferably carried out in a moisture-free atmosphere. For example, the reaction is preferably carried out in an inert gas atmosphere such as nitrogen.
Preferably, the preparation method comprises the following specific implementation modes:
(1) adding the non-aqueous solvent and the oxalic acid into a reactor, placing the reactor in an oil bath at the temperature of 60-70 ℃, bubbling and stirring the mixture by using an inert gas to obtain a homogeneous solution, dropwise adding the dichlorodimethylsilane into the homogeneous solution, heating to 50-100 ℃ after dropwise adding, carrying out heat preservation reaction for 80-100 hours, heating to 70-100 ℃ after the reaction is finished, degassing to remove impurities, and cooling to 10-30 ℃;
(2) and (2) adding the lithium hexafluorophosphate into the reactor in the step (1), bubbling by using an inert gas, and stirring and reacting at the temperature of 20-50 ℃ for 4-6 hours to obtain the lithium difluorobis (oxalato) phosphate solution.
The reaction equation of the invention is as follows:
first step reaction equation
Second reaction equation
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the preparation method is simple and practical, and can be used for industrial production, the prepared lithium difluorobis (oxalate) phosphate solution can be directly used as a non-aqueous electrolyte battery additive, and the prepared lithium difluorobis (oxalate) phosphate solution contains less chlorine compounds and free acids, wherein the chlorine compounds are less than 5 mass ppm by chlorine concentration, and the free acids are less than 200 mass ppm by hydrofluoric acid converted acid concentration.
Detailed Description
The following examples are intended to illustrate several embodiments of the present invention, but are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
In a nitrogen glove box having a moisture content of less than 20 mass ppm, a 1000ml three-necked flask containing a stirrer was prepared, 500g of diethyl carbonate having a moisture content of 10 mass ppm or less and 20.0g of oxalic acid having a moisture content of 200 mass ppm were charged into the three-necked flask, and the three-necked flask was sealed. The three-neck flask was transferred to the outside of a glove box, placed in an oil bath at a temperature of 65 ℃, equipped with a condenser tube, a constant pressure dropping funnel, inserted into a bubbler and slowly bubbled with nitrogen, and the bubbled gas was absorbed with water. The solution was stirred thoroughly using a magnetic stirrer until a homogeneous solution was formed.
Then, 43g of dichlorodimethylsilane was charged into a constant pressure dropping funnel, and dichlorodimethylsilane was dropped into the homogeneous solution in the three-necked flask for 30 minutes. After the end of the addition, the constant pressure dropping funnel was replaced with a glass stopper, and the temperature was raised to 75 ℃ and the reaction was maintained for 90 hours. After the incubation reaction was completed, the temperature was raised to 90 ℃ until the wet pH paper contacted the bubbling bubbles, the pH paper was neutral indicating that HCl had been completely removed, and the temperature was lowered to room temperature and transferred to a glove box. The absorption liquid is hydrochloric acid solution.
In a glove box, 17.2g of LiPF6The resulting mixture was added to the solution, the three-necked flask was transferred to the outside of the glove box, a condenser tube was attached, a bubbler was inserted and bubbled with nitrogen, and the bubbled gas was absorbed by a KOH solution. And stirring the solution at room temperature by using a magnetic stirrer to react for 5 hours to obtain the lithium difluorobis (oxalate) phosphate solution. The absorption liquid is subjected to phase separation to obtain linear polysiloxane liquid and KF aqueous solution.
Use of the obtained product19The product concentration in the solution was 4.2% by mass by F NMR, and the yield of lithium difluorobis (oxalato) phosphate was 80% by lithium hexafluorophosphate.
The chloride ion concentration in the solution was measured to be 1.8 mass ppm by the method of potentiometric titration.
The concentration of the free acid in the solution was measured by titration, and the hydrofluoric acid result was 65 mass ppm.
Example 2
The preparation was carried out in the same manner as in example 1 except that 51.6g of dichlorodimethylsilane was used, the molar ratio of the dichlorodimethylsilane to oxalic acid was 1.8, and dimethyl carbonate was used as a nonaqueous solvent19F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.9% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalato) phosphate was 75% as calculated by lithium hexafluorophosphate. The chloride ion concentration was 4.9 mass ppm, and the hydrofluoric acid concentration was 142 mass ppm.
Example 3
The same procedure as in example 1 was repeated, except that 37.3g of dichlorodimethylsilane was used, the molar ratio of the dichlorodimethylsilane to oxalic acid was 1.3, and dimethyl carbonate was used as a nonaqueous solventSynthesis was carried out in the same manner as in example 119F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.9% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalato) phosphate was 76% as calculated by lithium hexafluorophosphate. The chloride ion concentration was 1.4 mass ppm, and the hydrofluoric acid concentration was 89 mass ppm.
Example 4
The preparation of a lithium hexafluorophosphate was carried out in the same manner as in example 1 except that 20.25g of lithium hexafluorophosphate was used, the molar ratio of lithium hexafluorophosphate to oxalic acid was 0.6, and dimethyl carbonate was used as a nonaqueous solvent19F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.5% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalato) phosphate was 68% as calculated by lithium hexafluorophosphate. The chloride ion concentration was 1.9 mass ppm, and the hydrofluoric acid concentration was 21 mass ppm.
Example 5
The preparation was carried out in the same manner as in example 1 except that 15.18g of lithium hexafluorophosphate was used, the molar ratio to oxalic acid was 0.45, and dimethyl carbonate was used as a nonaqueous solvent19F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalate) phosphate was 57% as calculated as lithium hexafluorophosphate. The chloride ion concentration was 2.3 mass ppm, and the hydrofluoric acid concentration was 165 mass ppm.
Example 6
Synthesis in the same manner as in example 1 was carried out in the same manner as in example 1 except that the reaction temperature in the first step was changed to 90 ℃19F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.4% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalato) phosphate was 65% as calculated by lithium hexafluorophosphate. The chloride ion concentration was 4.9 mass ppm, and the hydrofluoric acid concentration was 59 mass ppm.
Example 7
Synthesis in the same manner as in example 1 was carried out in the same manner as in example 1 except that the reaction temperature in the first step was changed to 60 ℃19F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 2.4 mass% as calculated by NMRThe yield of lithium difluorobis (oxalato) phosphate was 46% based on lithium hexafluorophosphate. The chloride ion concentration was 3.2 mass ppm and the hydrofluoric acid concentration was 16 mass ppm.
Comparative example 1
Synthesis was carried out in the same manner as in example 1, except that the degassing temperature was changed to 60 ℃ in the same manner as in example 119F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.9% by mass as calculated by NMR, and the yield of lithium difluorobis (oxalato) phosphate was 76% as calculated by lithium hexafluorophosphate. The chloride ion concentration was 23 mass ppm, and the hydrofluoric acid concentration was 167 mass ppm.
Comparative example 2
Synthesis of second-stage reaction temperature in the same manner as in example 1, except that the reaction temperature was adjusted to 60 ℃ in the same manner as in example 119F NMR measurement, chloride ion concentration measurement, and free acid concentration measurement. The product concentration in the solution was 3.9 mass% calculated by NMR, and the yield of lithium difluorobis (oxalate) phosphate was 63% calculated as lithium hexafluorophosphate. The chloride ion concentration was 3.4 mass ppm, and the hydrofluoric acid concentration was 268 mass ppm.
The present invention includes but is not limited to the above embodiments, and those skilled in the art can convert more embodiments within the claims of the present invention.
Claims (7)
1. A preparation method of lithium difluorobis (oxalato) phosphate solution is characterized by comprising the following steps: the method comprises the following steps:
(1) reacting dichlorodimethylsilane with oxalic acid in the presence of a non-aqueous solvent to generate dimethylsilyl oxalate, wherein the non-aqueous solvent is diethyl carbonate and/or dimethyl carbonate, the water concentration in the non-aqueous solvent is less than 100 mass ppm, the concentration of the oxalic acid in the non-aqueous solvent is 1-20%, and the feeding molar ratio of the oxalic acid to the dichlorodimethylsilane is 1.2-1.6;
(2) adding lithium hexafluorophosphate into the reaction liquid obtained in the step (1), and bubbling with an inert gas to react to obtain the lithium difluorobis (oxalate) phosphate solution, wherein the feeding molar ratio of oxalic acid to lithium hexafluorophosphate is 1: 0.4-0.6;
the lithium difluorobis (oxalato) phosphate solution contains a chlorine compound in an amount of 5 ppm by mass or less and a free acid in an amount of 200 ppm by mass or less.
2. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 1, wherein: the reaction temperature in the step (1) is 50-100 ℃.
3. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 1, wherein: in the step (1), after the reaction of the dichlorodimethylsilane and the oxalic acid is finished, degassing and impurity removal are carried out.
4. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 3, wherein: the temperature for degassing and removing impurities is 70-100 ℃.
5. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 1, wherein: the reaction temperature in the step (2) is 20-50 ℃.
6. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 1, wherein: the preparation method is characterized in that the reaction is carried out in an inert gas atmosphere.
7. The method of preparing a lithium difluorobis (oxalato) phosphate solution as set forth in claim 1, wherein: the specific implementation mode of the preparation method is as follows:
(1) adding the non-aqueous solvent and the oxalic acid into a reactor, placing the reactor in an oil bath at 60-70 ℃, bubbling by using an inert gas and stirring to obtain a homogeneous solution, dropwise adding the dichlorodimethylsilane into the homogeneous solution, heating to 50-100 ℃ after dropwise adding, carrying out heat preservation reaction for 80-100 hours, heating to 70-100 ℃ after reaction, degassing to remove impurities, and cooling to 10-30 ℃;
(2) and (2) adding the lithium hexafluorophosphate into the reactor in the step (1), bubbling by using an inert gas, and stirring and reacting for 4-6 h at the temperature of 20-50 ℃ to obtain the lithium difluorobis (oxalato) phosphate solution.
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| CN109851640A (en) * | 2019-01-17 | 2019-06-07 | 兰州理工大学 | Double oxalic acid lithium phosphates of a kind of difluoro and the preparation method and application thereof |
| CN111943983B (en) * | 2019-05-17 | 2023-01-31 | 微宏动力系统（湖州）有限公司 | Preparation method of lithium oxalate phosphate solution |
| CN110240617A (en) * | 2019-06-19 | 2019-09-17 | 上海如鲲新材料有限公司 | A kind of preparation method of difluoro dioxalic acid lithium phosphate |
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| CN112919441B (en) * | 2019-12-06 | 2022-07-29 | 江苏国泰超威新材料有限公司 | Method for coproducing lithium difluorophosphate and lithium difluorooxalate phosphate |
| CN111606951A (en) * | 2020-05-14 | 2020-09-01 | 东莞东阳光科研发有限公司 | Method for preparing cyclic lithium salt solution, nonaqueous electrolyte solution and battery |
| CN113717227A (en) * | 2020-05-26 | 2021-11-30 | 恒大新能源技术(深圳)有限公司 | Preparation method of lithium difluorobis (oxalato) phosphate and derivatives thereof, electrolyte and secondary battery |
| CN114075104A (en) * | 2020-08-18 | 2022-02-22 | 恒大新能源技术(深圳)有限公司 | Method for producing oxalate phosphate, oxalate phosphate derivative, method for producing oxalate phosphate derivative, and electrolyte salt |
| CN112661791B (en) * | 2020-12-23 | 2023-09-22 | 多氟多新材料股份有限公司 | Preparation method of difluoro lithium bisoxalato phosphate |
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